A/6r/e—o3/?3 4$jef5'os<z/

COmPAAHIA BRAfllf IRA Df mfTAIIMCIA f miAIAACAO

IP

a COfltPAAHIA BRfi f l l f IRA Df AlfTAlURGIA f ffllAfRACAO

Heod Offke

Coixo Postal 8 38180 firaxo, MG - Brazil Phone: (034) 661.1544 Telex: (034) 3355 CBMM BR

Branch Offices

BRAZIL

Companhia Brasileira de Metalurgia e Mineração Rua Podre João Monoel, 923 - 9? andor 01411 • Sõo Paulo, SP - Brazil Phone: (Oil) 881.7100 Telex: (011) 25683 CBMM BR

euflope

Niobium Products Company GmbH. LUagnerstrasse 4 D-4000 DüsseWorf -1 litest Germany Phone: (211) 35.3404 Telex: (41) 8587006 NPC D

NORTH flMÍRICR

Niobium Products Company ltd. 440 Park LUest Bldg. Two Cliff Mines Road Pittsburgh, Pfl 15275 - U.S.A. Phone: (412) 787.9620 Telex: (230) 90.2936 NPC-PGH

ORIENT

CBMM Internacional flhosoka Brighton Bldg.,5th PI. 5-2, Rkasako 1 - Chome, Minoto-Ku Toku° '07 - Japan . Phone: (3) 586.3921 Telex: (72) 26616 CBMM J

Niobium Technical Report, NbTR - 03/83 ISSN-0101-5963 April (1983)

CATAIVTIC PROPERTIES OP OlODIUm compouriDS

K. TANABE and T. IIZUKA Hokkaido University Faculty of Science — Department of Chemistry Sapporo, Japan

Contents

Introduction 1 1 - Dehydrogenation and Oxidative Dehydrogenation I 2 - Ammoxidation Process and Synthesis of Alkylpyridines . . . . 2 3 - Reforming of Hydrocarbons 2 4 - Production of Polyester and Esters 3 5 - Polymerization 3 6 - Metathesis and Isomerization of Olefin 4 7 - Decomposition of Nitrogen Oxides 4 8 - The Catalyst Electrode for Fuel Cell 5 9 - Hydrocarbon Synthesis from CO and H-» 8

10 - Hydrogenation 10 11 - Oxidation 10 12 - Miscellaneous 13

Acknowledgment 15 References 15

FIGURES AND TABLES

Fig. 1 - Reduction of NOx with NH:{ 6 Fig. 2 - Cunent-potential curves 7 Fig. 3 - Activity of nickel catalysts 9 Fig. 4 - ti-2 chemisorption vs temperature of activation for

supported-iridium catalysts II

Table 1 - Oxydehydrogenation of Ethane 21 Table 2 - Oxidative dehydrogenation and dehydrogenation

hydrocarbons 22 Table 3 - Ammoxidation of Hydrocarbons 23 Table 4 - Synthesis of Alkylpyridines at 450°C 24 Table 5 - Reforming of naphtha 24 Table 6 - Polyester production reaction at 280°C 24 Table 7 - Polymerization of 1,3-butadiene 25 Table 8 - Polymerization of propylene 25 Table 9 - Conversion of hydrocarbons 25 Table 10-NOx + NH3 reaction NO:300 ppm, NH:i:450 ppm,

SO..:500 ppm, 02 :15% 26 Table 11 - Pt-Nb Electrode 26 Table 12 - Fischer-Tropsch Synthesis 26 Table 13 - Selectivity of several Ru catalysts 27 Table 14 - Hydrogenation of benzene at 160°C, 50 atm H_. 28 Table 15 - Production of methacrylic acid oxidation of methacrolein 28 Table 16 - Fluorination of benzotrichloride 29 Table 17 - Synthesis of diamond 29 Table 18 - Polymerization of Acetylene to Benzene 30

Introduction

This is a report prepared for CBMM. which outlines the catalytic activity and selectivity of niobium compounds including niobium oxides, salts, organometallic compounds, etc. The application of niobium compounds as catalysts to diversified reaction as seen in the content of this report is realized. The nature and action of niobium catalysts are characteristic and sometimes anomalous, suggesting the necessity of basic research and the potential use as catalysts for important processes in chemical industry.

1 - Dehydrogenation and Oxidative Dehydrogenation

The catalytic dehydrogenation or oxidative dehydrogenation of hydrocarbons has become of major industrial importance for the production of diolefins or aromatic vinyl compounds. However, the oxidative dehydrogenation of paraffin hydrocarbons has not been so successful. Recently, Thorsteinson et al.'" developed an effective catalyst for the production of ethylene from ethane by the oxidative dehydrogenation process. The catalysts consist of a mixture of the oxides of Mo and V with a variety of third metals. Among the most effective catalysts found were an unsupported material having the atomic composition M00.73 V„. l s Nb0.0!» and a material with the composition Mo,M{i V„.3t Nbo.ox when supported on a-alumina. The activity and selectivity are shown in Table 1. The product o\ci MoVNb catalyst at the temperature around 300°C was exclusively ethylene at I atm, but at higher pressure (=20 atm), acetic acid was obtained (selectivity =20%). In the reaction at 1 atm., molybdenum oxide itself h*s only a slight activity. The addition of vanadium does not increase the activity of M0O3 very much, but additions of both vanadium and niobium result in a very active and highly selective catalyst. Thus, the role of niobium in this system is important to obtain high activity and selectivity.

In the patent literatures, catalysts containing niobium compounds (mainly oxide) are reported to be effective for the oxidative dehydrogenation of ethylbenzene, ethylpyridine or diethylbenzene, butenes or butane and dehydrocyclization of n-heptane to toluene. n *' The data are summarized in Table 2.

Niobium Technical Report • NbTR • 05/ft'i • /

In the dehydrocyclization of paraffin, cerium oxide is known as a promoter to improve the activity and selectivity of Cr20:{-Al_>0:t catalyst, but niobium oxide was more effective for that purpose.'"

2 - Ammoxidation Process and Synthesis of Alkylpyridines

The use of vanadium oxides as catalysts in ammoxidation processes is well known. While less common, niobium oxides have also been reported for use in certain ammoxidation procedures. For example. Japanese patent No. 43-7610 discloses that unsupported catalysts consisting of mixtures of niobium oxide with tin or titanium oxide are useful for ammoxidation of alkyl substituted aromatic hydrocarbons to nitriles. For the ammoxidation of alkyl substituted aromatic compounds, th; catalysts consisting of TiO-_>, V20.-„ Nb- Or,. P-..0-.. KjO. CsjO were reported to be effective for the production of terephthalonitrile from p-xylene and ammonia.(8) An a-alumina supported vanadium alkali metal bronze promoted with niobium is also known as an effective catalyst for the synthesis of terephthalonitrile.'''"" For the production of unsaturated nitril such as acrylonitril from alkane and alkene molecules, the catalyst consisting of MoO:{. Mb-..0.-,. PjO:, etc. were reported.'" l2> The mixture of n-butenes and isobutene is also reported to be oxidized with air. NH:{. and H_.0 at 400°C over W. Nb. Ca. Bi. Mo/Al-jO^ or Mo,. s Bi, W„.:, C~ati Nb„.T to give 1.3-butadiene and methacrylonitril. The conversions of n-butenes and isobutenc were 93-95% and 92~96%, respectively and the selectivities for 1.3-butadiene and methacrylonitrile were 83-84% and 84%. respectively.1"' In the case of the reaction of propylene and nitric oxide to ptoduce acrylonitril. Bi O.!-Nb-_,Or,- PjO-, catalysts were reported in a U.S. patent."41 The data of ammoxidation are summarized in Table 3. For the production of alkylpyridines from acetaldi*hyde and ammonia, silica-alumina catalysts with Nb oxide. Sb oxidr or Ta oxide as a promoter have been reported as shown in Table 4. "'

3 - Reforming of Hydrocarbons

As a reforming catalyst, platinum supported on Al_»0:{ is well known. To improve the catalytic property of Pt/Al^.Os, many kinds of additives have been examined until now. In the patent literature, it was reported that the high octane value was obtained if niobium was added to Pt. Ir. CI/A1L.O ;{ catalyst in the reforming system.'"'I7' A Russian patent mentions that petroleum undergoes cracking over Nb. K/support at 775°C to form ethylene (32.0%), propylene (11.67r ). butadiene (3.5%). and butenes (3.9% )."8' The other patent stated that the addition of Nb or Ta and F to Pt/AI^O;{ was effective for the hydrocracking of n-heptane."1" The data are shown in Table 5.

2 • Niobium T:'chnkvl Report • NbTR • 03'«>

4 - Production of Polyester and Esters

Polyesters such as polyalkylencterephthalate are produced by the condensation reaction of terephthalic acid derivatives. Halogenated niobium compounds are known to show a high catalytic activity for this condensation. However, in some cases, the coloration of polyester products occurs by a side reaction with halogen compounds. To avoid the coloration, the hydrolyzed NbCl.-, was u«-'d as a catalyst in the reaction of dimethylterephthalic acid.'20' The hydrolyzed catalyst showed high activity and the product had high clarity. Niobium metal powder was also used to produce colorless polyester.'21' For the condensation of glycol ester, niobium or tungsten aryloxides are known to show high catalytic activity.'221 The data are summarized in Table 6.

As for the synthesis of esters, acrylic ester was obtained from aldehyde, aliphatic carboxylic acid, and aliphatic alcohol at 300°C over Nb...O.-, (10 m%)/AUO-A.

O O CH.

RCH.COH + R'OH + HCH -RCCOR' + 2H..O

6

With the -nolar ratio (2:1) of HCHO to CH:{CHO and that (1.9:2) of CH«OH to CH:,COOH and with 1.2 of flow rate. 31 % (based on acetic acid) of methyl acrylate was obtained.'•'^ Methyl acrylate was also obtained directly from formaldehyde and methyl acetate with NbL.Or. (10 wt%)/AL.O:i, the yield being 14%.'241 Ethyl acrylate can be obtained at 3I5"C from acrylonitril, water, and ethanol when Nb.-O-M0wt% )/SiO_> is used as a catalyst.l2,i| Methyl succinic acid mono and dimethylester is reported to be formed at 150°C from propylene (6 atm). CO (40 atm), 0 2 (20 atm) and CH:{OH with a catalyst consisting of Nb methylate. Cu acetate, KBr, and P(C«Hr,)».'*' The effect of Nb is much better than that of Ta or Ti Diacetoxy butene is reported to be formed from butadiene, sodium acetate, and acetic acid at 80°C over Pd.iSL-.Nb» Ciooo. the selectivity being 85% .,271

5 - Polymerization

Niobium compounds are known as polymerization catalysts for " the polymerization of olefin or diolefin. For example, a mixed catalyst of niobium trichloride distearatc. nickel naphthenate and tricthylaluminium can initiate the polymerization of 1.3-butadiene to obtain a liquid polymer. a" The Nb(Tt-C;,H.-,):( catalyst polymerizes butadiene at 30°C to yield 50% of polybutadiene, the microstructure being 100% of 1,2-type.(2"' In the case of TiCl2I2 + AlOdH,,)». however, the yield is 20% at 50°C and 92% of the microstructure is

Niobium Technical Report • NbTR • 03/83 • 3

1,4-cis type. For the polymerization of butadiene in aqueous emulsion state, Nb(IV) ion has polymerization activity as shown in Table 7.,30)

As a catalyst for the polymerization of olefin, Ziegler-Natta catalyst is very well known. The addition of metal halide to the Ziegler-Natta catalyst is reported to improve the activity and the crystalinity of produced polymers. ""

For the copolymerization of ethylene and propylene, the mixture of tetraaryl niobium and halogenized titanium was used as a catalyst.'" "' From ethylene (45 g) and propylene (HOg) mixture under high pressure (22 atm.) at 70°C, 55.4 g of gummy polymer was obtained. Niobium tetrachloride butanoate was also active for the polymerization of cyclic monoolefins.(34)

6 - Metathesis and Isomerization of Olefin

A catalyst active for the olefin reactions including olefin disproportionation which comprises a compound of niobium or vanadium complexed with NO and a selected complexing agent (e.g. benzoic acid) and combined with an organoalunriium compound (e.g. methylaluminium sesqui-chloride) was reported.(3M Niobium oxide is also active for the propylene metathesis at a high temperature (538°C). "<"

On the other hand, by using NbF.-, as a catalyst, a variety of hydrocarbon products was observed from the mixture of n-hexane and cyclohexane even at moderate temperatures (~50°C). , , 7 ) The mechanistic study of n-hexane homologation over Nb metal was also reported.,M) The data are summarized in Table 9.

1-Hexene and 1-hepvene are isomerized at 300°C with niobium hydride supported on SiO-.» to give 2-hexenes and 2-heptencs, respectively.,?9)

7 - Decomposition of Nitrogen Oxides

The catalysts for the decomposition of NOx in the industrial stack gas are very important to prevent the air pollution. In some cases, for the gases which do not contain SOx or dust, the catalyst systems are practically working in the industrial plant using NH3 as a reducing reagent. The most popular catalyst for this process is \-20-, supported on TiO^ which shows the practical activity at temperatures between 300 and 400°C. However, for coking furnaces or calcination plants in steel industry, the catalyst which posesses low temperature activity is demanded, because the emission gases are at temperatures lower than 300°C.

4 • Niobium Technical Report • NbTR • 03/83

The addition of Nb to the practical catalyst seems to be very effective to improve the low temperature activity in such a system. Japanese patents(4(MJ, showed that the catalyst containing Nb was very active at low temperatures (<200°C) compared to that without Nb component as shown in Fig. 1 and Table 10.

The addition of Nb is effective not only for the catalytic activity but also for the stabilization of catalyst at high temperature treatment to remove the byproducts such as acidic ammonium sulfate which deposited on the catalyst surface in the reaction.(44,45) The addition of Nb is also effective to improve the mechanical strength of the catalyst.,40) The catalyst which contains, V, Nb and other components of TI, Cu, Cr, W, Mo, Fe, Ni (at least one metal component of this group) showed high catalytic activity at low temperature region and also has the activity for the decomposition of excess unreactive NH3 gas.(41)

The catalyst for the direct decomposition of NOx without reducing reagent is reported in Japanese patent. (46) NOx should be decomposed to N.j and 0 2 at temperatures lower than 1000°C from thermodynamic view-point. However, the rate of decomposition is very low and the practical system has not been proposed. In the patent ,4*\ Nb or Ta metals or their compounds were reported to catalyze the decomposition of NOx at the temperatures of 300~800°C.

As for the catalyst for automotive exhaust gas, oxidation of CO. hydrocarbons and reduction of NO with a platinum metal catalyst cf the perovskite type such as [K] [Nbo.<»Pto.i]03, ISr] [Coo.?Nbo.i Ruo.alO» have been proposed.(47) The catalyst has the general formula ABO:i in which 1 ~50% of the B cation sites are occupied by cations of Pt, Pd, or Rh, —5% of the B sites are occupied by each of 2 oxidation states of a variable valence metal such as Nb, V, Co etc. and the remaining B cation sites are occupied by Al ions.,47)

The catalyst which consists of yttrium oxide, niobium oxide, lanthanum oxide, cerium oxide and iron oxide mixed with MnOj was also proposed for the automotive system.tm However. MnO-j is not recommended for use in such a system now.

8 - The Catalyst Electrode for Fuel Cell

A fuel cell is a primary battery wherein electrical energy is generated directly from the chemical energy of a combustible fuel by electrochemical reaction. Each fuel cell electrode comprises a conductor for the transport of the electrical energy generated in the cell in association with a catalyst for the half-cell reaction taking place at the particular electrode. Different catalysts are employed at each of the two electrodes in a given cell, since the half-cell reaction taking place at the oxygen electrode differs from the half-cell reaction taking

Niobium Technical Report • NbTR • 03/83 • 5

Fig 1 - Reduction of NOx with NHn. 1, TiOs-VsOs(5%)-NbíOsl2.7%). 2 i TiOj-ViOst" 5% )

6 • Niobium Technical Re/iori NbTK U~>'X~i

(A)

20

/iA/cm2

#

1

/

Nb

Pt

ÍT1V/H2

-100 100 300

<B)

2

1

5

A«A/cm2

• / / / / / / / / / / / 1 / # / 1 / 1 f

f"

Pt

/ , ' N •

D 20 5

DO 700 900 1100

mV/H2

f-ig. 2 • Current-potential curves. |A) H?Q-. fuel cell. (B)C .H4-0-j tuel cell

Niobium Technical Report - NbTR - 03/8~> • 7

place at the fue! electrode. Thus, the electrode should be conductive, corrosion resistant at high anodic electrode potentials in aqueous solution and good catalyst for the oxygen reduction reaction. The strontium niobium bronze of the formula Sr*NbC>3 and barium tantalum bronze of the formula Ba,:..-,Ta03 were proposed for that purpose. '*" Those bronzes may be utilized as such or in conjunction with a suitable conductive substrate, e.g.. porous carbon, metals, etc. Strontium niobium bronze of the composition Sr.Nb03. wherein x is a value between 0.70 and 0.95, were prepared. The powders were pressed into the form of an electrode, in admixture with nickel powder in a 1 to 2 volume ratio. The resultant electrode was tested as oxygen electrode in 1N NaOH supplied with gaseous oxygen at a pressure of ! atm. The logarithm of the current density obtained was linear with potential exhibiting a slope of 60 mV and an exchange current density of about 10 ' amps/cm2.

In an acidic electrolyte, Pt-Ti, Pt-Co, Pt-Nb alloys were used instead of Pt electrode by using H^, CH4, C ,H l 0 , C-,H12, C3HH, C>H(i. CNH, H etc. as a fuel.|50M| The alloy electrodes of Nb-Pt showed excellent activity compared to Pt black electrode as shown in Table 11.

As an anode of the fuel cell. Pt electrode is widely known as mentioned previously. In a French patent (52\ Nb metal or Nb oxide was used instead of Pt electrode. Pure niobium electrode showed a little bit higher activity than Pt in Hj-O^ fuel cell as shown in Fig. 2(A). If the fuel contains carbon such as ethane or ethylene, the electrode of niobium oxide is suitable for the purpose as shown in Fig. 2(B).

In the other patents, an intermetallic compound of nickel and niobium.,W) Nb^O-.-TiO^,,M) platinum deposited on an alloy of Ru and Nb. '" ' W-Nb carbide ,5*' are also reported to be effective for the electrode of the fuel cell.

9 - Hydrocarbon Synthesis from CO and H-»

The finite supply of natural liquid fuels has prompted a new interest in the synthesis of fuels from coal. A well known process in this regard is the Fischer-Tropsch synthesis of hydrocarbons from hydrogen and oxides of carbon. For the production of gaseous fuel from CO + H>, many catalyst systems have been proposed until now. Among them, Ni supported on Nb^O.-, or 1a>0:, was reported for the enhanced synthesis of paraffinic hydrocarbons with chain lengths from 2 to 6 carbon atoms.(l"' Niobium oxide supported Ni catalyst showed considerably higher activity compared to a conventional Ni/ AljO;{ catalyst as shown in Fig. 3 and higher selectivity for higher hydrocarbons as seen in Table 12. A catalyst of Ru/NbaOr,

(58) was

8 • Niobium Technical Report NbTR - 03/85

5000

4000

z U-0 Ç3

Z 2

ES

/

Q 3000

%

SIO

N

d LU > O ü 0 O 200Ú LL 0 LU ^-< X

1000

•

\

\ . *

% • % \

V

l i /Nb205

\ \

% \ %

" \ \ %

%

V % %

Ni/

V

\ —•

% \

\ 1 \ %

% • h

*tf>3\

1

280 270 260

TEMPERATURE °C

250

Fiçj 3 • Activity of nickel catalysts

Niobium Technical Report • NbTR • 03/83 • 9

also proposed to produce the higher hydrocarbons selectively. The data are shown in TabL* 13. Niobium oxide is known to show strong metal support interaction (SMSI) proposed by Exxon group.'5,1 M)l which modifies the property of metal component on the catalyst. As seen in Fig. 4. the adsorbed amount of hydrogen chemisorption on lr/NbL.0-, catalyst was drastically decreased when it was reduced at high temperatures. From the point of view mentioned before, the interaction of Nh._.0.-, support and metal component in the CO + HL> reaction will be very interesting and important to prepare highly active and selective catalyst.

10 - Hydrogenation

1-Hexene. 1-heptene. and cyclohexene were reported to be hydrogenated with hydrogen over nickel hydride supported on SiOL. to form lOO'/r of hexane. heptane, and cyclohexane, respectively, at 160. 150 and I00°C. "" The NbNi,,Co hydrogenates n-hexanc to form n-hexane at 145°C and the activity which is decreased by thiophene can be reactivated with hydrogen. The activity and the degree of reactivation are higher than British Petroleum catalyst and Ni:(Co. '*2' The hydrogenation of benzene to cyclohexane was found to be catalysed with Ni-Nb in liquid phase, the activity being high compared to Ni or Ni-Ti as shown in Table 14. " " The Ni-Nb catalyst is also active for the production of polyhydric alcohols by the hydrogenation of glucose and xylose at 1I5-120°C. 2 0 - 5 0 atm H... |M|

Benzalclehyde is easily reduced with ethyl alcohol to form benzyl alcohol at 20°C over Ni-Nb (5%), the reaction rate is 8 times higher than that over a simple Ni catalyst. '*'

11 - Oxidation

Acrolein, methacrolein, acrylic acid, methacrylic acid, maleic acid anhydride, phthalic acid, anthraquinone which are produced by oxidation reaction are important materials in chemical industry. Acrolein is used for manufacturing allyl alcohol, pyridine, 3-picoline, acrylic acid, acrylonitril. an DL-methionine. Acrylic acid is an important monomer for manufacturing homopoiymer and copolymer which are widely used as paint material, adhesive agent, material to improve paper and textile, and finishing material of leather. Methacrylic acid is important for manufacturing methacryl acid methyl ester which is a monomer of acrylic glass. Maleic acid anhydride is used for improving unsaturated polyester resin and for manufacturing phthalic acid esters which arc used as a plasticizer. Anthraquinone is an important intermediate in dye synthesis and is i-sed also for production of hydrogen peroxide.

10 • Niobium Technical Report • NhTR - 03 #3

Fig. 4 • H-j chemisorption vs temperature of activation for supported-indium catalysts. H/M = atoms hydrogen adsorbed at 25C,C per atom iridium present in catalyst; 7 = temperature of activation in hydrogen; wt% Iridium = 1 for SiOL., AljO : l, V-..0,, and HfO^ and 2 for all other catalysts.

Niobium Technical Report • NbTR • 03/83 • II

Ill- Acrolein and methacrolein

Acrolein is obtained by the oxidation of propylene with air. When FeSbs.ti:<Oi 4.4/SiO_. is used as a catalyst, the conversion is 28% at 471°C. However, the addition of 7.2% Nb to the catalyst causes to increase the conversion to 38% under the same reaction condition. "*' A complex oxide, Nb0.2 W,,..- Co.-, Bii Fe0.4 M12 K„.«>« Si]

.:{."•• was presence of water vapor at 315°C. The conversion of propylene was found to be also active for the oxidation of propylene with air in the 98.5% and the selectivity for acrolein formation was 46.1%. the other product being acrylic acid.,67'

Methacrolein is obtained by the oxidation of isobutene with air over the catalysts containing Nb. The Mo,2 Bi» Nb, Tei catalyst was most active for the oxidation, the conversion of isobutene and the selectivity being 88.3 and 83.6%, respectively, at 460°C.<*,) The Mo,_. Nb, Sb, Te2 04 0-4-/Si02 is reported to give 95.5% of conversion of isobutene and 73% of the selectivity for the formation of methacrolein together with methacrylic acid at 375-415°C. '*970,

11.2 - Acrylic acid and methacrylic acid

Acrylic acid is easily obtained by the oxidation of acrolein with air over the catalysts containing Nb. With a Mo,2 V:i Nb2 Fe, Si;..-, catalyst, the conversion of acrolein was more than 90% and the selectivity for the formation of acrylic acid was 91.8% at 210°C. n , )

In the case of a Moi() Nb7 Fei Cu, Si,2..-(/a-Al20;{ catalyst, the conversion and the selectivity were 96.6 and 93.8%, respectively, at 250°C. ,72> The MoO rNb20;;Si02 catalyst gives 81% of acrylic acid at 417°C, the conversion of acrolein being 77.3%. ,73,74) According to German patent, the conversion was 97.6% and the selectivity of acrylic acid was 92.6%at 305°C when Mo2.4 V(,.:t Nb„.:< Fc,,.«3 Cun.o» Co,,.on Cr0.o3 Mno.o:</Si02-Al20:{ was used as a catalyst. Acrylic-acid is also obtained directly by oxidation of propylene with air. The selectivity of acrylic acid was 63.1% at 400°C over MoO:rNb20.-,-As2G :{/Ti02, the other products being acetic acid and acrolein.(76 "' According to a Japan patent, the conversion of propylene and the selectivity of acrylic acid are 99.6 and 73.7% at 325°C with Nb0.-> W,,3 Co.-, Bi, Fe„,4 Mo,, K,MH} Si,.3.-..

(67'

Methacrylic acid is produced by the oxidation of methacrolein with air in the presence of water vapor over the catalysts containing Nb as shown in Table 15. , 7 8"' It is seen from the Table that Mo,2 P2 Nb2.4 Cs2 Ti,,., 04*., (No. 4) and Tl2 Mo12 IníSn, P, 0 4 4 (No. 7) show high actvity as well as high selectivity and Mo,2 Pi» Nb2>4 K2 04„ (No. 5) shows the highest selectivity, though the activity is not so high. The Mo12 P, Nb, Cs0.2 catalyst is reported to exhibit 84.1% of conversion and 91.0% of the selectivity for methacrylic

12 • Niobium Technical Report • NbTR - 03/83

acid when the composition of gas (methacrolein, air and water vapor) is changed (8I). Mitsubishi Rayon's patent mentions that the activity as well as the selectivity is markedly lowered when Nb and Cs (alkali) are removed from Mo, . P2 Cs, Nb, V, Cu„..-, (No. 18).(83) In fact, Nb and Cs seem to be important components of the oxidation catalysts (notice the activity and selectivity of Mo,;> P, V, 0 4 H (No. 10) catalyst). Methacrylic acid is synthesized also by the oxidation of butyric acid and the selectivity for the formation of methacrylic acid are 53 and 53% at 350°C, respectively.l84)

11.3 - Maleic acid anhydride

The oxidation of 2-butene with air is reported to be catalyzed at 406°C by V..,O.vP20r,-Nb20-,/alundum to give 88 wt% yield or maleic acid anhydrid. ,85) The catalyst calcined at low temperature (300°C) is said to have long life. Maleic acid anhydride is also obtained by the oxidation of butadiene with air at 320°C over Nb, Mo,/SiC, the conversion of butadiene and yield of maleic acid anhydride being 100 and 55 mol %, respectively.,86)

11.4 - Phthalic acid

Terephthalic acid is obtained by the oxidation of p-xylene at 180°C with a catalyst consisting of Co, Mn. Nb + HBr-CH:{COOH. the yield of terephthalic acid being 94%.(87) Phthalic acid anhydride is formed by the oxidation of o-xylene at 400°C over VjO.--Nb_.0-, catalyst(M) or by the oxidation of acenaphthene at 360°C over V_05-TiO_- K_0-Cs_.0-P_0.--Nb_0;( catalyst.<m The yield is 120 wt% in the latter case.

11.5 - Anthraquinone

Anthraquinone is obtained by the oxidation of anthracene with air over TiO.-V.O.vCs.O-KjO/SÍC, the yield being 110.5 wt% at 420oC.'90, It is also produced by the oxidation of l-methyl-3-phenylipdan with air by the following scheme.

o + 9 O. • 2 C l C j O + 2 CO. + 2 CO + 8 H.O

A catalyst, V._Os-Sb20„-Tl_0-TeOs-Nb_Or„ gave 78.5 wt% yield of anthraquinone at 442°C. ""

12 - Miscellaneous

Niobium compounds are widely used in the related field of catalysis. Especially, niobium halides "2 W) were used for the

%

Niobium Technkal Repon - NbTR • 03/83 • /5

halogenation of hydrocarbons as shown in Table 16. Niobium fluoridel95> is also used for the decomposition of hydrocarbons deposited on the deactivated Friedel-Crafts type catalysts to reactivate it.

Niobium carbide is used as a catalyst of the synthesis of diamond from carbon. '* 971 Most effective catalyst has the composition of 50% NbC and 50c/r Cu as shown in Tabic 17.

For the production of heat resistant mattrials with large suface area l98). niobium carbide, boride or nitride was mixed with aluminum, silver, copper, cobalt, nickel or iron and heated at 1200°C—2000°C, then the metal components were dissolved by hot acid. The surface area of produced material is almost 10—50 m2/g.

Niobium metal supported on mordenite or acid clay was used as a catalyst for the disproportionation of toluene to produce benzene and xylene and for the trans alkylation of toluene and trimethyl benzene to produce xylene.''"" However the effect of Nb for the reaction was not clearly elucidated.

For the production of benzene from acetylene, Nb^O.-, supported on Al20;rSiO.».ZrO^-SiO.. or SiOj was found to be highly active compared to other transition metal oxides""01 as shown in Table 18.

3-Acetylenic alcohols are isomerized to ethylenic carbonyl compounds by heating with a catalyst of Nb Cl.-,.(lün

R' ^ C * C - R ' R' R' j : c^T * :;C = CH-CO

A mixture of 8.8 g of dehydrolinalool. 0.428 g of catalyst containing 48 mg of niobium and 40 cm' of Vaseline oil is heated for 3 hrs at 14()°C in a dry atmosphere. After distillation, citral is obtained with a degree of conversion of 70.6% and in a yield of 5.9% based on the dehydrolinalool converted.

Niobium catalysts (chloride, sulfate, phosphate, acetate ethoxide etc.) are known to catalyse the rearrangement of allyl alcoholtK2) as well as other transition metal compounds such as V, W, Ta, Mo. A super acid. NbF.-, + HF, catalyses the reaction of toluene at 200°C to form benzene, cthylbenzcne, xylenes, and cumene.nm>

Nickel-niobium metal catalyst was used for the hydrogenolysis of maleic acid anhydrid to 1,4 butane diol and tetrahydrofurane no41 as well as Ni. Mo. W. Zr metals.

Niobium naphthalate was reported to catalyze the epoxidation of propylene with t-butylperoxide etc. "nv "*• m7'

14 • Niobium Technical Report - NbTR - 03. 8>

Acknowledgment

This survey is based on more than one hundred patents and several scientific papers. The authors gratefully acknowledge the help of Dr. S. Kado. CBMM, for supplying the patents.

References

1 - E. iVl. Thorsteinson, T. P. Wilson, F. G. Young and P. H. Kasai. "The oxidative dehydrogenation of ethane over catalyst containing mixed oxides of molybdenum and vanadium", |. Catal. 52 (1978) 116-132.

2 - J. F. McMahon, "Oxidative dehydrogenation catalysts containing niobium". U. S. Patent No. 3371125 (1968).

3 - J. F. McMahon, "Vinyl aromatics from ethyl aromatics with a chromium-niobium catalyst", France Patent No. 1500632 (1967).

4 - K. Beccu, H. Buchner and M. Gutjahr, "Metal carbide dehydrogenation catalyst". Ger. Offen. No. 2250023 (1972).

5 - L. Bajars. "Dehydrogenating hydrocarbons", U. S. Patent No. 3291854 (1966).

b - L. Bajars, "Oxidative dehydrogenation process", U. S. Patent No. 3308196 (1967).

7 - R. C. Hansford, "Catalytic dehydroeyelization of heptane to toluene". U. S Patent No. 5480684 (1969).

8 - T. Ohara. M. Ninomiya, T. Nakamura and T. Ono, "Aromatic nitriles". lapan Patent No. 74-34673 (1974).

9 - R. D. Bushick and H. P. Angstadt, "Ammoxidation of m- and p-xylene". U. S. Patent No. 3959536 (1976). R. D. Bushik and H. P. Angstadt, "Ammoxidation catalysts for xylenes". U. S. Patent No. 4018713 (1977).

10 - R. D. Bushick and H. P. Angstadt, "Ammoxidation of m- and p-xylene to nitriles", Neth. Appl. No. 7413110 (1974).

11 - G. A. Castellion, "(Meth)acrylonitrile by catalytic ammoxidation", Ger. Offen. No. 2232360 (1972).

12 - B. Scherhag, A. Hausweiler, K. Schwarzer and R. Stroh, "Preparation of methacrylonitrile by reaction of isobutylene with ammonia and oxygen", Ger. Offen. No. 1235297 (1960).

13 - S. Umemura, K. Ohdan, Y. Bando and T. Hisayuki, "Catalysts for oxidation of butenes and isobutene", lapan Patent No. 78-27713 (1978).

14 - ). M. Kruse, "Catalysts for preparation of acrylonitrile from propylene and nitric oxide", U. S. Patent No. 3342847 (1967).

15 - C. W. Hargis, "Catalytic vapor-phase synthesis of alkylpyridines", U. S. Patent No. 3829428 (1974).

16 - M. Michel, "Platinum-containing catalyst for hydrocarbon conversion". Ger. Offen. No. 2338113 (1973).

17 - M. Michel, "Catalyst containing platinum for conversion of hydrocarbons'.' France Patent No. 2196192 (1972).

18 - S. V. Adel'son, A. P. Smirnov, V. J. Gurevich, E. M. Rudyk, V. I. Nikonov, Ya. M. Paushkin and B. L. Ivankovskii, "Olefin hydrocarbons". U. S. S. R. Patent No. 410073 (1974).

19 - R. C. Hansford, "Catalytic dehydrocyclization of heptane to toluene", U. S. Patent No. 3480684 (1969).

20 - T. Tsuji, "Stereospecific polyesters", lapan Patent No. 70-40310 (1970).

Niobium Technical Report - NbTR - 03/53 • /5

21 Y. Itabashi and K. Nakayama. "Polyesters with good whiteness", lapan Patent No. 72-08225 (1972).

22 - M. Wada and K. Yocia. "Catalyst for polyesterification". lapan Patent No. 71-12153 (I97i).

23 - C. N. Wolf and |. F. McMahon. "Acrylic esters". U. S. Patent No. 3535371 (1970).

24 • C. N. Wolf and J. F. McMahon. "Acrylic ester production from formaldehyde and an alkyl ester with niobium oxides as catalyst", U. S. Patent No. 5440276 (1969).

23 - C. W. Hargis, "Esters of unsaturated acids from the corresponding nitrites". U. S. Patent No. 3466320 (1969).

26 - W. C-aenzler, K. Kabs and C. Schroeder, "Hydroformylation catalysts for ester manufacture". Ger. Offen. No. 2529577 (1975).

27 - T. Matsuda. T. Shirafuji and H. Danda. "Diacyloxybutenes from butadiene". Japan Patent No. 79-14914 (1979).

28 - R. H. Gaeth. "Catalyst for producing liquid polymers". U. S. Patent No. 3557075 (1971).

29 - S. I. Beilin. S. B. Gol'shtein. B. A. Dolgoplosk and E. I. Tinyakova. "Organometallic compounds as catalysts or catalyst components for the polymerization of butadiene". U. S. S. R. Patent No. 591478 (1978).

50 - H. Naarmann and E. G. Kastning. "1.5-Polydienes in aqueous emulsions". Ger. Offen No. 1258092 (1965).

31 - K. Tashiro. M. Yokoyama and S. Kitazume. "Olefin polymers", lapan Patent No. 74-15651 (1974).

32 - K. Tanaka and H. Konuma. "Ethylene-propylene copolymerization". lapan Patent No. 71-45890 (1971).

55 - K. Tanaka and H. Konuma. "Catalysts for ethylene-propylene copolyme­rization". lapan Patent No. 72-01283 (1972).

3 4 - 1 - E. Burleigh and C. A. Uraneck. "Use of amine promoters in the catalytic polymerization of cyclic monoolefins". U. S. Patent No. 5640986 (1972).

55 - W. B. Hughes and E. A. Zuech. "Complexes of vanadium or nitrogen or niobium containing nitric oxide with organo-aluminums. as olefin reaction catalysts". U. S. Patent No. 5562178 (1971).

56 - R. L. Banks. "Olefin conversion catalyst". U. S. Patent No. 5442969 (1969).

37 - M. Siskin and I ). Porcelli, " Isomer ization of aliphatic hydrocarbons", U. S. Patent No. 5948761 (1976).

58 • C. O'Donohoe, |. K. A. Clarke and J. J. Rooney, "Homologation of n-alkanes on metal films - A novel aspect of metai-carbene chemistry". |. C. S. Faraday Trans. I. 76 (1980) 345.

39 - V. U. Lunin and S. I. Serdyukov, "Catalyst for hydrogenation and isomerization of unsaturated hydrocarbons" U. S. S. R. Patent No. 584886 (1977).

40 - F. Kurozawa. "Catalyst for nitrogen oxide removal from waste gas", lapan Patent No. 79 52692 (1979).

41 - H. Utsunomiya, K. Soga, K. Shimazaki, Y. Mito, M. Aoki. S. Haseba, H. Miki and M. Masaki, "Catalysts for the removal of nitrogen oxides from waste gases". Ger. Offen. No. 2634279 (1976).

42 - H. Utsunomiya, K. Shimazaki. K. Soga, Y. Mito and M. Aoki, "Denitration catalyst". Japan Patent No. 77-151688 (1977).

43 • S. Haseba, S. ho, Y. Mito and T. Hirano, "Waste gas treatment catalyst", Japan Patent No. 80-28718 (1980).

44 - K. Shimazaki and S. Haseba, "Denitration of sulfur oxidecontaining waste gas", lapan Patent No. 79-51970 (1979).

/6 • Niobium Technical Report - NbTR - 03/83

45 - H. Utsunomiya, K. Shimazaki and S. Haseba, "Catalytic removal of nitrogen oxide from waste gases", Japan Patent No. 77-31970 (1977).

46 - K. Oodan, H. Sasaya, K. Yoshida and H. Otsuka, "Catalytic decomposition of nitrogen oxides". Japan Patent No 73-55870 (1973).

47 - A. Lauder, "Catalytic composition with perovskite crystal structure". Ger. Offen. No. 2518537 (1975).

48 - O. Kamigaito, H. Doi. K. Sano and T. Kandori. "Catalyst for reduction of nitrogen oxides", Japan Patent No. 75-06589 (1975).

49 - B. P. ). Bockrts. D. Sepa and A. Damjanovic. "Barium tantalum and strontium niobium bronzes as catalysts for oxygen reduction at the cathode in fuel cells". U. S. Patent No. 3553025 (1971).

50 - ). G. E. Cohn, O. |. Adlhart and K. O. Hever, Fuel cell". France Patent No. 1440445 (1965).

51 - Engelhard Industries, Inc.. "Improvements in or relating to fuel cells", British Patent No. 1070604 (1965).

52 - M. Bonnemay. G. Bronoel, D. Doniat and E. Levart. "Oxidation catalysts for fuel cells", France Patent No. 1526907 (1966).

53 - L. R. Dilworth. "New catalysts for fuel cells". France Patent No. 1476048 (1966).

54 - V. Mehra and W. R. Wolfe. Jr.. "Fuel cell and process for producing electric current using titanium dioxide catalyst". U. S. Patent No. 3505118 (1970).

55 - O. J. Adlhart and A. J. Hartner. "Fuel cell having catalytic fuel electrode". U. S. Patent No. 3475224 (1969).

56 - Battelle-lnstitut E. V., "Electrodes with mixed metal carbide catalyst, for hydrogen fuel cells". France Patent No. 2005568 (1969).

57 - E. L. Kugler and S. |. Tauster. "Catalyst comprising nickel supported on tantalum oxide or niobium oxide and their use as hydrocarbon synthesis catalysts in carbon monoxide-hydrogen reactions". U. 5. Patent No. 4206155 (1980).

58 - M. A. Vannice and S. J. Tauster. "Catalytic manufacture of olefin hydrocarbons from carbon monoxide and hydrogen", Ger. Offen. No. 2845294 (1978).

59 - S. J. Tauster, S. C. Fung and R. L. Garten, "Strong metal-s-jpporl interactions. Group 8 noble metals supported on TiOs". J. Am. Chem. Soc. 100 (1978) 170.

60 - S. ]. Tauster and S. C. Fung, "Strong metal-support interactions. Occurrence among the binary oxides of group IIA-VB", J. Catal. 55 (1978) 29.

61 - V. V. Lunin and S. I. Serdyukov, "Catalyst for hydrogenation and isomcrization of unsaturated hydrocarbons", U. S. S. R. Patent No. 584886 (1977).

62 - N. S. Barinov, G. M. Strashnova, I. I. loffe, D. V. Mushenko, V. S. Fedorov and V. S. Zavgorodnii, "Catalyst for hydrogenation of unsaturated compounds", U. S. S. R. Patent No. 491400 (1976).

63 - F. B. Bizhanov, N. I. Popov, D. V. Sokol'skii, E. B. Bakhanov and A. M. Khisametdinov, "Cyclohexane", U. S. S, R. Patent No. 246491 (1976).

64 - F. B. Bizhanov, D. V. Sokol'skii, A. K. Omarov, S. O. Ongarbaev, A. M. Khisametdinov and N. I. Popov, "Preparation of alditols". U. S. S. R. Patent No. 196766 (1967).

65 - D .V. Sokol'skii, F. B. Bizhancv and N. I. Popov, "Benzyl alcohol", U. S. S. R. Patent No. 201362 (1967).

66 - f. L Callahan. P. K. Grasselli and W. R. Knipple, "Promoted antimony-iron oxidation catalyst", U. S. Patent No. 3546138 (1970).

67 • I. Nagai, I. Yanagisawa, M. Ninomiya and T. Oohara. "Oxidation of propylene", lapan Patent No. 76-04113 (1976).

Niobium Technical Report • NbTR • 03/83 • 17

68 - Y. Oda, K. Uchida. M. Suhara and T. Morimoto. "Oxide catalysis for acrolein and methacrolein manufacture". Ger. Offen. No. 2508782 (1973).

69 - T. H. Vanderspurt. "Selectively oxidizing isobutylcnc to methacrolein and methacrylic acid". U. S. Patent No 4195187 (1980).

70 - T. H. Vanderspurt. "Selective oxidation catalyst". U. S. Patent No 4184981 (1980).

71 - Y. Watanabe. M. Imanari. N. Nojiri and N. Fuga. '"Acrylic acid from acrolein". Japan Patent No 75-93918 (1975).

72 - Y. Watanabe. M. Imanari. N Nojiri, N. Fuga and M. Nakajima. "'Acrylic acid"', lapan Patent No. 74-153517 (1974).

75 - R. Parthasarathy and F. G. Ciapetta. "Catalyst consisting of mixed oxides of niobium and molybdenum and its use in the oxidation of acrolein and methacrolein". U. S. Patent No. 5557199 (1971).

74 - R. Parthasarathy and |. G. Ciapetta "Catalyst for oxidation of acroleins and methacroleins". France Patent No 1555159 (1969).

75 - H. | . Decker and E. M. Thorsteinson. "'Unsaturated aliphatic carboxvlic acids'. Ger Offen No 2601699(1977).

76 - H. S. Young. G. C. Anderson and F.. L. iVlcDaniel. "Catalysis for acrylic acid preparation from propylene". France Patent No. 1489656 U967).

77 - H. S. Young. G. C. Anderson and E. L. McDaniel. "Catalysts for manufacturing acrylic acid", France Patent No. 95250 (1970).

78 - T. Shiraishi. H. Ichihashi and T. Shirafuji. "Oxidation catalyst in the production of methacryiic acid by oxidation of methacrolein in the gas phase with oxygen'*. Ger Offen No 2517148 (1975).

79 - Y. Oda. K. Uchida. T. Morimoto and 5 Kumai, "Melhaervlic acid". Ger. Often No. 2514252 (1975).

80 - Y. Oda. K. Uchida and T. Morimoto. "Unsaturated carboxvlic acids'. lapan Patent No. 75-49715 (1975).

81 - M Kawakami. H. Yamanouchi. I. Nishiwaki and Y. Yoshida. "Unsaturated carboxylic acids", lapan Patent No 75-70517 (1975).

82 - S. Akiyama and A. Yamamoto. "Acrvlic acid and methacrvlic acid", lapan Pateni No. 77-151118 (1977).

85 - M. Olani, H. Matsuzawa, M. Kobayashi and H. Ishii. "Acrylic acid and methacrylic acid", lapan Pateni No. 77-68122 (1977).

84 - f). W. McNeil and B. Phillips. "Conversion of saturated aliphatic acids and their derivatives with at least 4 carbon atoms into the corresponding unsaturated compounds". Cer. Offen. No. 2856509 (1979).

85 - R. O. Kerr. "Catalyst for the preparation of dicarboxylic acid anhydrides'.' U. S. Patent No. 5551565 (1967).

8b - T. Shirasaki, K. Moriya and I. Furuova. "Malcic anhydride". |apan Pateni No. 76-143613 (1976).

87 - K. Teranish. T. Iio. K. Kawamoto, H. Fukuhara and Y. Zenitani. "Aromatic carboxylic acids by liquid-phase air oxidation", lapan Patent No. 76-127034 (1976).

88 - Yu. V. Kiriehenko. G. N. Kirichenko. A. Kh. Sharipcv, R. M. Masagutov. T. M. Khannanov and I. I. Shabalin. "Catalyst for oxidizing hydrocarbons", U. S. S. R. Pateni No. 255202 (1970).

89 - Y. Nanba. T. Suzuki, Y. Nakanishi and Y. Okuda. "Catalysts for oxidation of acenaphthene lo 1,8-naphthalenedicarboxvlic acid anhydride". Japan Pateni No. 75-59292 (1975).

90 Y. Nanba. T. Ono and Y. Okuda, "Anthraquinone bv catalytic anthracene oxidation". Ger. Offen. No. 2304685 (1973).

91 - M. Sprague, H. Wistuba. H. Engelbach. H. \. Sturm and H. Armbrust. "Catalysts for anthraquinone manufacture by l-methvl-5-phenvlindan oxidation". Ger. Offen. No. 2160781 (1973).

18 • Niobium Technical Report - NhTR • 03/«5

92 • I.. P. Sendlak. "Liquid phase lluorination". U S. Patent No. 4129602 (1978).

^ Y. Oda and M. Suhara. "Pentafluoroethyl iodide". Ger. Offen. No. 2150096 (1972).

94 - H. A. Pacini. A. H. Pavlath. E. C. Teach and F. H. Walker. "Fluorinations with arsenic trifluoride'. U. S. Patent No. 3287424 (1966).

95 R. Hulme. Recovery of tantalum and/or niobium pentafluoridcs from a hydrocarbon conversion catalyst*'. U. S. Patent No. 4065405 (1977).

96 - Tokyo Shibaura Electric Co., Ltd.. "Diamond synthesis". British Patent No. 1119624 (1968).

97 - Tokyo Shibaura Electric Co.. Ltd . "Artificial diamonds". Neth Appl. No 6610609 (1967).

98 - Robert Bosch G. M. B. H.. "Manufacturing of hard materials of large specific surface, as carbides, nitrides, borides. suicides, useful as abrasives, adsorbents, catalysts'*. France Patent No. 2015619 (1970).

99 - Y. Sato and H. Takahashi. "Catalysts for disproportionate. transalkylation. and isomerization of alkylaromatic hydrocarbons*', lapan Patent No. 74-59797 (1974).

100 - Lab. Catal. Amoy Univ.. "Coordination catalysis by compounds of transition metals. I. Supported chromia and niobia catalysts and mechanisms of catalytic cyclotrimerization of acetylenes". Scientia Sinica 17 (1974) 26-46.

101 - P. Chabardes and Y. Qucrou. "Ethylenic carbonyl compounds". U. S. Patent No. 5920751 (S975).

102 - Y. Ohmura, Y. Ninagawa. Y. Fujita. T. Hosogai. T. Nishida, Y. Tamai and K. Itoi. "3. y -Unsaturated alcohols". )apan Patent No. 75-58004 (1975).

105 - M. Siskin and |. |. Porcelli, "Acid cetalyzed conversion of aromatics to alkyl aromaiics", (J. S. Patent No. 5728411 (1975).

104 - |. Ramioulle and W. Couteau. "1.4-Butanedior*. Ger. Offen. No. 2752156 (1978).

105 - H. Friedrkli. W. Heim. A. Kleemann. H. Kolb and G. Schreyer. "Separation of epoxidation and hvdroxylation catalvsts from distillation residues'*. Ger. Offen. No. 2454572 (1976).

106 - Halcon International Inc.. "Method for the simultaneous preparation of epoxide of Gt — Ci alkenes and styrene derivatives", Neth. Appl. No. 7515858 (1975).

107 Halcon Internationa) Inc.. "Epoxy compounds". Neih. Appl. No. 7514558 (1975)

Niobium Technical Report - NbTR • 01/M • 19

Table 1

OXYDEHYDROGENATION OF ETHANE Activity and Selectivity of Molybdenum Catalysts

Temperature ("O Selectivity (%) Temperature <UC) Selectivity <%) Mixed oxide compositions for initial to C2H4 for 10% to C2H4

activity. T„ at Tu conversion. Tin at Tlu

Mo».7sVo.|gNbo.iMi Mou.7dVu.17Ti8.BiMnB.iM Mo».««V«.i7Ta«.«wFe».ii3Sia.M Moo.73Vo.iHNbtt.01sMnu.iMx Mo«.wtVu.i«Wo.o«Mno.iB M08.7uVo.17Tio.esNbo.3Mno.iM Moo.70Voj7Nbo.09Cuo.u4s Moo.70Vo.17Tao.ooMno.045 Mo».7»V».nTao.«»Fe«.Q4s Moo.sMno.j Mo0.g3Nbej0W0.00Mn0.ii Moo.7«Vo.i»Feo.oi Moo.jjWo.is Moo.ttTio.i Mo«.7sNbo.i«Wo.oo Moi.o Moo.oiVo.od Moo.s7Bio.osTio.uMno.! 1 Sio.n Mo..7*W,. , .Pb,. , Moo.ttVo.j Moa.«V»,i7Mn(U7 Moo.8Nb«,i

215 215 220 243

<255 260 260 309 310 320 328 370 388 390

- 4 0 0 418 444 460 474 500 502 516

100 100 100 100 100 84 95 85

100 100

- 1 0 0 100 100 100

— 100

- 1 0 0 100

> 8 0 100 100 100

286 295 289 300 295 400 330 385 418

550-600 400 435 650 600 524 500 562 505 588 i>40 505 634

100 100 100 100 100 80 78 63 97 35 10 87 78 65 67 88 59

100 72

100 100 74

Table 2.

Oxidative dehydrogenation and dehydrugenation of hydrocarbons.

3- Catalyst c' 3

Reacliun Reaction

temp. CO Conversion Selectivity %

to stylene Ref.

I I 2:

50

l.0WO;t-0.6NbsOr.

I.OWO.-1-l.CNbsO»

l.0Cr ;O3-2.0Nb2Os 1.0CiiO3-0.6Nb2Os I OCrjOa - 1 0Nb;O5 - 0.2KiO

I .OCriOa - 4NbiOj - 0.15KjO

NbCx(C:46 atomic °o) TcCx(C:42 " ) ZrC:;(C 48 " )

NbsOj/Alundum

NbsO» NbiOs+5%LiCI 70£"oAlsOa- 50%CriOa

" + 5%KsO 70%AlsOa-27.5%CriO;,-2.5%Nb.O5

+ 5%KsO + 5%CaO + 5%SrO

ethylbenzcnc + Oj (Cap.V.0.7-1.0V/hr/V)

ethylpyridine + Oj

ethylbenzene (?cm3/min)

isobutanc + O» butane/steam/oxygcn =1/10/0.85 HC1/butane = 0.115 2 —methyl butene —2 + O*

2-butene + 0 2 + HBr

n — heptane

675 700 675 700 700 700 700 650 625

600 M

** 450

450

700 700 557* 510* 453* 461* 455* 448*

47 56 43 54 58 63 83 67 51

(to vinyl pyridine) 11 7

20

isobutene was

isobutene was

85 84

obtained

obtained

84 83 83 83 84

82-85 59.8 89.9 81

65 75 71*» 85*» 64** 76** 75** 83**

2) 2) 2) 2) 2) 2) 2) 2) 2)

4) 4) 4)

5)

5)

6) 6) 7) 7) 7) 7) 7) 7)

*) Temperature for 25"<' conversion **) Selectivity °i> to toluene

Table 3.

Ammoxidation of Hydrocarbons

Catalyst Reaction Reaction

temp. rC> Conversion % Ref.

c' 3 -J

a-

2 ;

so

TiOi:ViOs=(97.«i:2.l)-l\.O3(0.49wt%)K.iO(0.146")NbsO5<0.244- >

l iO.-ViO r . /SiO NasViOs - NbsOs/o - Al sO s

<X = 0~1 . Vi05:8.5%, Nb-Os^.b"»)

MoOs - NbsOs- PiOj/SiOj (11.9) (3.01) (4.9)

MoOs- BijOs- PiOs/AliOa (9.5) (2.4) (5.8)

WOs-CuO-NbaOs

B i i O a - N b s O s - P i O s - N i O (2) (1) (1) (2)

BiiOs-PaOs BiiOs-TiOj

p—xylene + NHs + air (0.6) (4.8) (94.6)

p-xylene + NHS + O s

1 : 3.2 : 3.0 p-xylene 4 NHS + O.

1 : 3.2 : 6.0

propane + NHa + air

isobutene + NHs + air + H 2 0

propylene + NO + N2

383

430

485

485

435

435 490

terephthalonitrilc p — toluonitrile 80.1 3.2

72.5

propane 33

44

meihacrylic acid nitrile

43

acrylonitile 85

82 76

8.3

acrylonitrile 24

54

8)

395 395 430

84.5 65.3 65.0

1.5 3.3

25.2

8) 8)

9.10)

9.10)

ID

11)

12)

12)

12) 12)

Catalyst

Si0,-AI._,0:,

Si02-Al203 + Nb,0, (10wt%)

Si02-AI20,+Sb20, + K20

Table 4

Synthesis of Alkylpyridines at 450°C

Reaction 2-Picoline V l ^ ^ * ) Other Pyridines

Acetaldehyde+ NO 15.5 14.1 10.1

20.2 18.5 13

31.9 26.3 9.7

Table 5

Reforming of naphtha (aromatics 9 wt%, naphthen 29 wt%, paraffin 62 wt%)

Catalyst Reaction temp. (*C)

Pressure (bars)

Octane Value Ref.

Pt, Ir, Nb, CI/AljO, (0.35%) (0.05%) (0.15%) (1.2%) Pt. Ir. C1/AI203

485 530 485 530

25 10 25 10

93 104 91.2

102.5

15) 15) 15) 15)

n-Heptans reaction

Catalyst

Pt.Nb,F7AI,0 Pt.Nb/AIjÕ, Pt,TB.F/AI20, Pi/Al,,0,

R taction temp. <*C)

350 350 350 350

Total conversion

%

87 45 90 32

Conversion to aromatics

%

1 9

23 8

Conversion of isomerization

%

40 12 35 10

16) 16) 16) 16)

Table 6

Polyester production reaction at 280°C

Catalyst

NbCl5

Nb305

Hydrolyzed NbCI5

Nb metal powder Sb203

Niobium penta-phenoxide Tungsten hexa-phcnoxide

wt %

0.0070 0.0034 0.0046 0.02 0.03

0.056

0.074

Time

— — —

4 (hr) 3

40 (min)

40 (min)

Viscosity

0.63 0.62 0.64 0.66 0.67

0.88

0.53

Color of product

yellow i*

white L=79.6 (clarity) L=73.3 (clarity)

—

—•

24 • Niobium Technical Report • NbTR • 03/83

Metal ion

Ti(IV) Cr(lll) Nb(IV) Mn(lll) Ge(lV) Ta(IV) Mo(V)

Yield (%)

35 32 36 56 41 38 41.5

Polymerizat

1.4-cis(%)

38 46 25 52 29 33 43

Table 7

ion of 1,5-butadiene

Metal ion

Pd(ll) Rh(IIl) La(III) Ce(!V) Tl(Ill) Au(lll) Th(IV)

Yield (%)

37 52 39 50.5 40.5 54.5 46

l,4-cis(%)

16 41 24 21 20 "»5 22

Table 8

Polymerization of propylene (TiCl4 + Triethyl Al + Metal halide)

Catalyst

NbCls/TiCI4 =0.017 BeClz/TiCI4 =0.017 MnCL/TiCI4=0.017 GeCl4/TiCi4=0.017 RuCl3/TiCl4=0.017 TeCI4/TiCl4 = 0.017 TiCl,

Catalyst Reactant

[(Da(NO)bMcZdlx pentene M:Nb or V, Z: hydrogen L:Ligand

Polymerization rate

28.9 29.1 33.4 33.3 36.8 28.2 30.4

Table 9

Conversion of hydrocarbons

Reaction temp. (°C)

Crystalinity of polymers (%)

98.3 98.6 98.3 98.3 97.4 98.9 92.8

Products

room temp, butenes (1.7 wt%) + hexenes (2.1 wt%)

10% NbaOs/SiO» propylene 1000°F

NbF, + HF + H, n-hexane <37.6g)(20g)(100psig.) +cyclo

hexane

5CC (I hr)

Nb melal n-hexane 186-C

224'C

C'j(2.l%),(C,.((96.3°/o), 1-C'4(0.5%) t-C'.(0.5%). C-C'4(0.3%). C".(0.3%) Selectivity to ethylene and butenes = 90% C,(0.I1). i-C4(0.07) i-C.(0.06), i-C5+n-C5(0.07) 2,2-dimethyl C,( 11.92) 2,3-dimethyl C. + 2 methyl Cs(35.75) 3 methyl C5(12.59), n-C.(27,87) methylcyclo C.(1.27) cyclo C.(6.82) benzene(3.45) C, + C*(40.2), C»(18.7), i-C,(0.2), n-C,(20.3), i-C;(0.4), n-Cn(19.0), C-Cid.2), i-C.(trace)

C, + C2(3I,6). C.,<18.7). i-C.(0.3), n-C.(19.6), i-Cs(0.3), n-C,(20.8), C-C»(l.6), i-C,(0.8), benzenc(5.5), n-C»(2.2)

Niobium Technical Report • NbTR • 03/83 • 25

Table 10

NOx +NH3 reaction NO:500 ppm. NHS:450 ppm. SO2:500 ppm. 0S:15%

CatalvsC Initial conv. After 15 hr,

(%) After 30 hr,

(%)

TiOrVaOs-NbsOs TiOj-VsOj

99

40

94

12

89 7

Table If

Pt-Nb Electrode

Composition of anode catalyst Potential in mV vs AgCl/Ag electrode at indicated current density in mA/cm-

0 5 10 20 30 50

Alloy of 30% Nb-70°c Pt Pt alone

100 130 150 200 240 300 90 240 280 540 380 430

Table 12

Fischer-Tropsch Synthesis

Selectivity of Nickel Catalysis (Reaction Conditions: H»/CO = 3 . Pressure 103 kPa)

1% Ni/Ta2Os

1% Ni/NbjOs 1% Ni/Al203

1% Ni/TajOs \% Ni/Nb2Os

1% NÍ/AI2O3 \% Ni/Ta2Os

1% Ni/NbjCV 1% Ni/AliOs 1% Ni/Ta205

1% Ni/NbiOs* 1% Ni/AljO;,

Temp. CO

275 276 273 266 268 268 257 258 262 249 250 252

% CO Conv.

11.1 6.4 6.6 8.1 4.9 4.5 6.6 8.3 3.2 3.4 7.2 1.9

Ci

58 60 88 50 54 87 45 48 88 40 47 88

c2

17 18 9

18 20 11 19 18 12 20 20 12

Products (Wt. %) Ca

trace

trace

c« 7 6

— 10 7

— 12 9

— 16 9

—

C,

4 3

— 6 4

— 8 8

— 7 7

—

c6

trace trace

— trace trace

— trace trace

— trace trace —

All rections were conducted at about 2400 hr ', except those with*, which were conducted at 1200 hr '.

26 • Niobium Technical Report • NbTR • 01/83

Table 15.

Selectivity of several Ru catalysts. (Reaction conditions: Hj/CO = 5: Pressure = 105 kPa)

5" 3

a-3

I -S3

la­'s

Catalyst

Ru-Melal <o

4 ^ Ru/Carbon>b>

\% Ru/StOi"»!

5"V Ru/Si i«"

\<"o Ru/Al i0 3 « a )

5% Ru/Al jOa , a )

1 % Ru /Nb iOs u >

1 % Ru/NbsOs u )

Temperature ("C>

226

243 234

232

235

228 244

259 234

244

"«CO

5.5

2,3 1,6

4.1

16.7

8.8 14.1

15.6 7.8

5.7

CH4

96

98 98

87

86

66 71

67

48

41

C Í H 4

0

0 Ü

1/2

trace

1/2

.12. .11 .

It

.14.

CjH«

4

2 2

6 1/2

7 1/2

10

Obtained hydrocarbons (mol.

CsH« CJHH

trace

trace Ü

4

4

8 1/2 7

6 1/2

12 1/2 18

C | H M C4H10

0

0 Ü

1

1 1/2

6 5

8 1/2

9 1/2 11

C j H i o C5H12

0

0 0

1

1

4 1/2 4

4 1/2

7

11

%)

CV

0

0 0

trace

trace

J 2

3

12 5

Cs-Cs Olefyn

0

Ü

0

2 1/2

trace

11 10

— 22 27

tv 4

2 2

n 14

34 29

33

52 59

(a) Catalyst reduced 1 hour at 450"C prior to introducing starting material (CO+Hj). <b) Catalyst reduced I hour at 400"C prior to introducing starting material, (c) Catalyst reduced I hour at 300"C prior to introducing starting material. CB+ hydrocarbon with 6 or more carbon atoms. C*+ olefvn hydrocarbon with 2 or more carbon atoms.

Table 14.

Hydrogenation of benzene at 160°C. 50 atm H»

Calalvst 20 Cyclohexane (%)

40 60 min

Ni Ni -Ti Ni-Nb(l% Nb)

20 23 34

59 45 67

61 68

100

Table 15.

Production of methacrylic acid b) oxidation of methacrolein

No.

1 2 5 4 5

6 7 8 9

10

I I 12

13 14 15

16

17 (8

Catalyst

MoiiP2Nb2.4CsiOw

MoijPaNbjCsjOu MoiaPiTaiViCsiOu M012P2Nb2.4Cs2Tln.1OM.!

MO|2P2Nb2.4K204H

TI2Mo,2NbiFe,Pi044 TlsMoi2ln|SniP1044 Tl2Moi2ZriNb|P|045 TI2Moi2Nbtln,P044 Mo,2P,V,04:1

Mo„.Nb,P, MoiiBiiNbtPi

Moi:P,Nb,Sb,

MoijP|Nb|Cs0.2 MoiiP,NbiTl».2

MouPiCsjBio.sNbii.j

MoiiPiCsaNb^n, MoiiPgCsiN^VjCuo.j

Reaction temp. (»C)

550 560 360 568 540

340 340 340 340 340

340 340

370 370 370

405 405

530 330

Conversion i%)

90.3 86.0 81.2 90.1 71.4

78 95 77 97 47

62 82.5

78.3 77.8 73.3

75 75.1

(after 30 days)

81.6 82.6

Selectivity Co) Methacrylic

acid

79.7 75.1 70.3 81.2 91.2

84 81 78 68 56

73.8 75.6

73.4 75.9 75.5

65.1 65.0

(after 30 days)

81 83.2

Acetic acid

9.0 9.7

16.6 4.0 5.0

9 7 9 6 7

8.2 7.3

Ret.

78) 78) 78) 78) 78)

79) 79) 79) 79) 79)

80) 80)

81) 81) 81)

82) 82)

83) 83)

2S • Niobium Technical Report - SbTR - 05 /«3

Table 16

Fluorination of benzotrichloride

„ , % weight of ^"•'J*' catalyst

NbCU "

TaCIs Reds

0.5 1.4 0.18 0.19

Temp. <"C)

48-52 66-72 55-59 57-59

Production of perfluoroalkyliodide from

Nb NbFi AlFs CaFs

Catalyst

50%NbC-50%Cu 50%NbC-5O%Ag 50%Nb-50%Cu 50%Nb-50%Ag 50%NbC-50%Au 50%Nb-50%Au 50%NbC-25%Ag-

0.10 0.10 0.10 0.10

•25%Cu

l»C) 75 ** »•

Benzotri-fluoride

77.2 95.5 94.0 60.1

Products Benzodi-fluoride

21.4 0.2 3.8

39.8

Benzofluoro-dichloride

0.1 — — —

perfluoroalkene. iode and iode penta-fluoride C.Fjl yield

(%) 97 " 66 54

Table 17

Synthesis of diamond

Pressure (atm)

71,000 " >» r t

** »»

Temp. <°C)

1,800 " n

n

" "

Time (min)

15 ** ft

» " n

n

Diamond produced (mg)

11.4 6.2

10.4 1.2 5.8 0.8

11.3

Niobium Technical Report • NbTR - 03/83 • 29

Tabic 18 Polymerization of Acetylene to Benzene

Active Component

Carrier Maximum Activity Reaction (C - CJiJg

Temp. ("C) catalyst)

CrO,

Nb.O;>

TaOF,

v;o5

MoO,

TiO..

ZrO,

AI..O;i-SiO,

ZrO.-SiO, SiO,, large-pored AU>a-StO.. + Sr ' -Al.O.-SiO,. KAc treated A l . O - S i O , (Steam-treated at 250*0

AljO^-SiOi Zr0 2 -SiOi SiO.. large-pored

AijOs-StO;

AliO^-SiOi

AI.O : ,-Si02

AI,0 , -S iO,

SiO,

120

no 120 85 85 85

170 140 120

200

270

220

550

- 3 5 0

8.3 5.4 3.1 5.5 8.3 4.5 4.6

7.8 b.4 to.4

5.5

1.0

0.2

Trace

Nil

30 • Niobium Technical Report - NbTK - 01/»J